Water-soluble aminostilbene derivatives and process



Patented Sept. 11 1951 WATER-SOLUBLE AMINOSTILBENE DERIVATIVES AND PROCESS Franz Ackermanm Binningen, Switzerland, as-

signor to Ciba Limited Swiss firm Basel, Switzerland, a 1

No Drawing. Application November 16, 1948, Se rial No. 60,399. In Switzerland December 12, 1947 13 Claims. (Cl. 260-509) According to one feature of this invention new amine derivatives are manufactured by substituting an SO3H group or a group (R1=H, alkyl, aryl, or furfuryl) or a neutralized -SO3H group or a neutralized in at least one amino group of amino compounds (with the exception of amino-coumarins and amino-naphthalene sulfonic acids) which contain at least one primary or secondary amino group attached to a nucleus and which when, in the form of a solution, applied to a substratum, in particular cellulose, fiuoresce blue to violet in ultraviolet light.

According to a further feature of this invention the new amino compounds are applied inindustrial processes, in particular as optical bleaching agents.

Fiber materials are improved, in accordance with this feature, by applying thereto, at a suitable pointin their process of manufacture or finishing, new amine derivatives as above set forth.

The new compounds have no dyestuff character but according to the constitution possess a more or less outstanding affinity for various substrata. On account of this property the products obtained according to the invention which in daylight or ultraviolet light have a blue to violet fluorescence have such an improving effect on materials to which they are applied that in the case of undyed material the whiteness is enhanced and in the case of dyed material the dyeing becomes brighter. In the case of undyed originally yellowish material the increase of the whiteness is due to the fact that the blue to violet fluorescence of the compound applied causes the originally yellowish material to appear white.

By introduction of SO3H or groups, and particularly of neutralized SO3H or groups into the amino groups of the starting materials in accordance with the process of the invention the solubility in water is increased. In addition the fastness properties, in particular the fastness to light of the fibers treated with the end products of this process may experience an improvement.

The starting materials for the preparation of the new amine derivatives may be aminostilbenes of the general formula wherein Ar stands for a divalent radical of the benzene series containing at least one sulfonic acid group linked to the benzene nucleous and, if desired, other substituents such, for example, as halogenor alkyl, Ari stands for a divalent radical of the benzene series which may contain groups imparting solubility in water, such as sulfonic acid groups, and also halogen and/or alkyl, :1: and 1,! each stand for hydrogen or alkyl, and n and m stand for 1, 2 or 3, that is for whole numbers amounting to at most 3.

Especially suitable for the preparation of the new amine derivatives are amino-stilbenes of the general formula groups, and the like, and, finally, aminostilbenes of the general formula r H H-NAr,o-NAr oH=OH-Ar-It--ABATFH wherein Ar and Ari have the above indicated meaning and may represent, for example, a phenylene radical.

Compounds of the general formula I groups into the amino group of the starting mate for example, are readily obtainable starting, ma.- m rials can, for example, be effected in the following terials. In this formula, at least one a in each manner: benzene ring stands for -SO3H and at the most (a) Radicals of the formula one 2 in each benzene ring stands for hydrogen, H and m, n, a: and 11 have the above indicated so meaning. 15

To these compounds belong, for example, com- 1 pounds of the general formula wherein R1 stands for hydrogen, alkyl, aryl or o H l H 0 cwl'q p bcnl- 03H 03H I wherein m, n, a: and y have the above indicated furfuryl and Me stands for alkali, can be intromeaning. duced into the amino group'of the starting mate- The following amino-stilbenes are mentioned rials by treatment with water-soluble aldehydeas specific examples: 4:4-bis-[4-amino-benzoylbisulfite compounds, such as are obtained, for amino] -stilbene-disulf,onic acid-(2:2); 4:4"bisexample, from aqueous alkali bisulfite solutions [4-amino-benzoylam1n0] stilbene tetrasulfonic and aldehydes. By treatment with formaldehyde acid-(2:2':6:6') 4:4"- bis [-4 N-methylaminobisulfite compounds, for example, by heating the benzoylamino] -stilbene-disulfonio acid (222') specified amino-compounds with-an aqueous sodi- 4:4-bis- ['3-aminoben,zoylaminol -stilbene-disulum formaldehyde bisulfite solution to 95-100 C., fonic acid- (2:2') 4-l'4-amino-benzoylamino]-4 radicals of the formula [(4-amino-benzo-ylamino) benzoylamino] stilv bene disulfonicac'id, (2:2'); 4:4 bis [4- (4- amino'benzoylammo) benzoyla'mmo] n in which Me has the significance set forth above, disulfomc 316M422) formula can. be introduced into the amino groups, In-

stead of formaldehyde. bisulfite compounds also 0 H o H HMQtQLIQg L 40 bisulflte compounds of other aldehydes such as acetaldehyde, benzaldehyde or furfural can be.

employed in similar manner;

(bl Radicals of the formula-SOaH can be in- E'? E troduced into the amino. groups of the starting HzNQ Q 5 aterials by treatment with the additionproducti I 03H of sulfurtrioxide or ahalogen sulfonicacid, such as: ohlorosulfonic acid, with pyridine, advantaalso the amino-stilbene-disulfonic acid of the geouslyinthe-presence of: an. excess of pyridine.

formula The above named sulfonating agents may be 0 V 0 o Q Q v t It it v.'

' SOaH 0 0 o HZN-QtL-N-Q -NQ -N H it t e l and substitution products of the amino-stilbenes 80- designated as sulfonating agents Which-replace a mentioned, whose aromatic rings may contain. hydrogenatom of an amino group by a SO3H- additional sulfonic acid groups, halogen atoms, group.

or alkyl radicals. Thewater-solubility of.- the products; of the in The introduction in accordance with the inventionis enhanced by the subsequent convervention of the SOaH groups or the sion of the water-solubilizing sulfonic acid groups.

H into their water-soluble salts, preferably alkali J so H} salts, ammonium salts, or salts withamines, un- 8 lesssuchsalts are. directly. obtained inithe process.

1 1 of manufacture.

groups, or the neutralized SO3H groups or m The mtroductmn or the neutralized H H -f-S OaH-gIOIlDS l- S0 H 1 1 into the amino groups of the aforedescribed wherein Ar stands for a divalent radical of the" benzene series containing at least one sulfonic acid group linked to the benzene nucleus and, if desired, an additional substituent such, for example, as halogen or alkyl, Ar1 stands for a divalent radical of the benzene series which may contain water-solubilizing groups of the benzene series, such as sulfonic acid groups, and also halogen and alkyl, R stands for hydrogen or alkyl, n and m for whole numbers amounting to at the most 3, and z for one of the radicals-S OaI-I,

-H-s0nsr, oHso,H, or OHSO3H lkyl ryl Examples of the products of the invention are those of the general formula 1 H o H 0 I l r" HOaS-CH-NAI1- wherein Ar stands for a divalent radical of the benzene series containing a sulfonic acid group in 2-position, and An for a divalent radical of the benzene series, preferably a phenylene radical, and their water-soluble salts of alkalis, ammonia, or amines. Other examples are compounds of the general formula,

wherein Ar stands for a divalent radical of the benzene series, preferably a phenylene radical containing a sulfonic acid. group in 2-position, and An stands for a divalent radical of the benzene series, preferably a phenylene radical, as well as their water-soluble salts of alkalis, ammonia, or amines.

Moreover, the present invention comprises the products of the general formula wherein Ar stands for a divalent radical of the benzene series, preferably a phenylene radical, containing a sulfonic acid group in 2-position, and An stands for a divalent radical of the benproducts tr this invention Moreoven the new products, in particular such as arederived from 4 4'-diamino-stilbene disulfonic acid-(2 :2) can be employed-"for the after treatment of printed cellulosic materials. I;

In general, formaldehyde bisulfite condensation products of diamino compounds which contain the atomgrouping may be introduced into discharge printing pastes for cellulosic materials.

The compounds obtainable in accordance with the presentp-rocess can also be employed in the course of the manufacturing process of the materials to be improved, them to'a paper pulp. p v

In general, small quantities of the products obtainable accordingto the inventio'n sufiicein order to attain an improvement of the materials.

The compounds obtainable according to the presentp-rocess can also be employed in admixture with'auxiliaryagents'such' as areemployed for the improvement of fibrous'material's, for example, together with washing agents (for example, in conjunction with soaps, salts of sulfonated washing agents, as for example, sulfonated benzimidazoles substituted on the 2-carbon atom by higher alkyl radicals, or also of mono-carboxfor example, by adding yli'c esters of 4-sulfophthalic (acid with higher fatty acids with aliphatic hydroxyor amino- 1 is obtained when zene series, preferably a phenylene radical, and

their water-soluble salts of amines.

The application in industry of the new products obtainable in accordance with theinvention can take place in such a' manner that the materials to be improved are soaked in solutions, in particular, aqueous solutions of the specified compounds and after hydro-extracting or squeezing out are dried. For example, white goods, in particular, after a washing process carried out in the customary "manner, can be after-treated with the alkalis, ammonia and sulfonic acids). In this manner the materials to be improved can be simultaneously washed and bleached. A particularly noticeable brightening undyed vegetable fibers, in particular cotton are treated with such mixtures con-- taining washing agents 1 As materials which can be. improved according to this process may be mentioned, for example, the following: Nitrogenous natural and artificial-materials such aswool, silk or synthetic polyamide fibers; also cellulosic materials. such as cellulose, paper, textile materials of cotton, linen, regenerated cellulose including staple fibers of regenerated cellulose; and finally synthetic materials such, for example, as are produced by polymerization. The best efiects'by the'application of the present process are, however, obtained on vegetable fibers. The material to be improved can be employed in any desired form, for example, in fiber form or also in the form of film. 1 The material can, for example, be undyed, dyed or printed. The following examples illustrate the -inven' tion, the parts and percentages being by weight unless otherwise stated and the relationshipof partsby weight toparts by volume being the same as that of the kilogram to the liter:

Example 1 40 C. parts of gmm with sodium chloride. mm... and the residue washed with aqueous sodimn chloride solution and dried.

The resultant compound at the formula is 2. Dale powder which is soluble in water When the solution is applied to colorless cellilhaving very similar properties is obtained.

' Example 2 To 50 parts-of i 'iidm at a temperature below chlorst fl'fonie acid added, and thereupon 4 :parts of -4: 4'-bis-l-4-amino- 3 the i'ormula sulfonic acid-(2:2')

aminollo-stflhene-disulionic acid-(2:23 the corquantity :of -4 :-4-'-iois-[4-methy1aminob'enzoylaminol stil-bene-disulfonic acid is used as starting material, the resultant compound has andis characterized by very similarproperties.

Example 3 A formaldehyde bisulfite solution is produced from parts of 40 per cent. sodium bis-ulfite solution and 162 parts of 3'? per cent. formaldeis hyde solution. The resulting solution is, rentiered Weakly alkaline with sodium carbonate.

To this are added 6 parts of the disodium salt of "4-amin'o-4Jamino-benzoylanfinoi-stilbene di- The whole is heated for one hour to boiling and evaporated to dryness. The resultant product is the compound of the formula 'SCHNB benzoylamino]-sti1bene-disnlonicncid (2:12'.) :are in the form of a yellow powder which is easily also added. temerature is to 90 .C. and maintained 401' one hour at @0415 1C. fathereupon the whole is allowed to cool, water, neutralized with sodium :wnd

the condensation roduct 'se'pamtcd with a saitso ing out agent, .101 example, new compound has the some soluble in water. Cellulosic materialto which a solution thereof .is applied, when exposed to ultraviolet light has a "bluish fluorescence.

I! there is employed instead of the disodium salt .o'f l-anlino-A-l[aminobenzoy1amino]-stilbene disulfonic acid-(2:2), the disodium salt of It is -flltered 6ft, Washed with aqueous 4 [4 amino benzoy1amino]-4"-[4-(4-aminochloride solution and dried. n 1m eoloreil powder is obtained which as delimit 111 water. Whe'n'the soiirtion isappi to-vihfliepiipen'l-this, on exposing th ultraviolet gives a mesh fluorescence.

or aim-m1 or the An w-team obenw ibenzoylunime 'benzoylaminoi] :stilbene disulionic aciii 2:-2"') or the disodi-um salt of "414 his E4 (4 -aminobenzoy1amino) benzoyl- 5 amino] -sti1bene-disu1fonic acid-(222'); the compounds of the formula until the starting material has disappeared. The

ish fluorescence.

If in lieu of 4:4'-bis- [4-amino-benzoylaminol- H H 1i respectively, are obtained. These have very similar properties.

Also the compound of the formula stilbene-disulfonic acid-(2:2), the sodium salt of 4:4'bis [4 amino benzoylamino] -stilbenetetrasulfonic acid (2:2' 6:6) or of 4:4 bis- Qt Q Q Q S O NB may be used as starting material.

Example 4 A benzaldehyde sulflte solution is produced [4 methylamino benzoylamino] stilbene disulfonic acid-(2:2') is used as starting material, the compound of the formula S O;Na S OgNa a I.

H i H O Na from 52 parts of 40 per centsodium bisulflte sorespectively, is obtained. The compounds have very similar properties. I

Example 5 From 52 parts of 40 per cent. sodium bisulfite solution and 19 parts of furfurol, a furfurol bisulfite solution is prepared which is. then rendered weakly alkaline with sodium carbonate. To it are added 6 parts of the disodium salt of 4:4-bis-[4 amino benzoylaminol-stilbene disulfonic acid- (2 :2) and the whole is boiled under reflux for about 1 hour, that is tosay until the lution, 21.2 parts of benzaldehyde and 50 parts of Water and it is rendered weakly alkaline with aqueous sodium carbonate solution. To it are added 5 parts of the disodium salt of 4:4'-bis- [4 amino benzoylamino] stilbene disulfonic acid-(222) and the whole is boiled under reflux whole is allowed to cool, treated to complete separation with sodium chloride, filtered, and the residue washed with sodium chloride solution and dried. The compound of the formula is obtained in the form of a light colored powder which is soluble in water. When this solution is applied to colorless cellulose paper this, when exposed to ultraviolet rays, assumes a blustarting material has disappeared. The solution is. allowed to cool, the condensation product separated with sodium chloride, filtered and the residue washed with aqueous sodium chloride solu- 75 tion and dried.

The resultant product of the formula OaNB I on: H

is a yellowish, water-soluble powder. tion when applied to colorless cellulose paper exhibits a bluish fluorescence in ultraviolet light.

Example 6 To a paper pulp containing 100 parts of paper in a hollander are first added 2 parts of resin size and after minutes 0.1 part of the product obtained according to Example-1, paragraph 1, dissolved in water. After a further 15 minutes 3 parts of aluminum sulfate are introduced. The paper mass treated in this manner is then passed through a mixer, to the paper machine.

The paper treated in this manner possesses a higher degree of whiteness than the untreated material.

Example 7 A cellulose fabric dyed with 4 per cent. of the dyestuff of the formula is printed with the following discharge preparation:

170 grams of sodium formaldehyde sulf oxylate, 510 grams of gum thickening 1:1,

1 gram of the product obtained according to Example 1, paragraph 1, 319 grams of water.

1000 grams The printed material is dried, steamed, rinsed and again dried.

The discharged portions possess a higher degree of whiteness than is obtainable without the addition of the above-mentioned product.

Example 8 Regenerated cellulose staple fiber is treated on the foulard with a bath which contains in addition to the customary substances necessary for the attainment of a crease-proof effect, 1 gram per liter of the condensation product obtained according to paragraph 1 of Example 1. This treatment after the customary working up of the material has the effect not only of imparting a crease-proof efiect but also an outstanding brightening.

What is claimed is:

SOzNa soluble derivative of an aminostilbene, which The solu- 10 comprises reacting an aminostilbene of the general formula L 1.1!: A L 1..

wherein Aris a member selected from the group consisting of a divalent phenylene radical containing a sulfonic acid group in the 2-position and a divalent phenylene radical containing a sulfonic acid group in the 2- and another sulfonic acid group in the 6-position, Ar being otherwise free from substituents, Ar1 is a divalent phenylene radical free from substituents, a: and y are members selected from the group consisting of H and alkyl, and n and m are whole numbers amounting to at most 3, with a watersoluble condensation product from a watersoluble acid salt of sulfurous acid and a member selected from the group consisting of formaldehyde, acetaldehyde, benzaldehyde and furfurol.

2. A process for the manufacture of a watersoluble derivative of an aminostilbene which comprises condensing an aminostilbene of the general formula wherein Ar is a divalent phenylene radical containing a. sulfonic acid group in the 2-position and being otherwise free from substituents, Arr is a divalent phenylene radical free from substituents, a: and y are members selected from the group consisting of H and allgyl, and n and m are whole numbers amounting to at most 3, with a water-soluble condensation product from a water-soluble acid salt of sulfurous acid and a member selected from the group consisting of formaldehyde, acetaldehyde, benzaldehyde and furfurol.

3. A process for the manufacture of a watersoluble derivative of an aminostilbene which comprises condensing an aminostilbene of the general formula H I i 1. A process for the manufacture of a water- (5 0 1 d i ative 0 a am n sti bene which com-.-

prises condensing the aminostilbene of the consisting of a divalent phenylene radical conformula I taining a sulfonic acid group in the 2-position with a water-soluble condensation product from I and a divalent phenylene radical containing'a a Water-soluble acid salt of sulfurol S. a nd sulfonic acid group in the 2- and another sulfonic a member selected from the group consisting of acid group in the 6 ps1t1on, Ar 'g otherwise formaldehyde acetaldehyde benzaldehyde and free fromsubstituents, Ari is a divalent phenylene furfurol. 1 v r 5. A process for the manufacture of a waterradmal free m substlments' R 15 member soluble salt of the aminostilbene derivative of selected from the group consisting of H and the formula lower-alkyl, n and m are whole numbers amountwhich comprises condensing 4:4-di-(4-aminomg to at most 3 and z is a'member selected benzoylamino) stilbene disulfonic acid (2:2') from the group consisting of v with a water soluble condensation product from a water-soluble acid salt of sulfurous acid and formaldehyde. f

6. A process for the manufacture of a water- 80 soluble derivative of an aminostilbene which comprises condensing the aminostilbene of th formula and s -cH-som l i i w" I I HBNQ -FIN-Q-NHQ-CH C 9. A water-soluble alkali salt of an amino- E v i, v p I 4o stilbene derivative of the general formula I n] I [ll I1 with a water-soluble condensation'product from L a water-soluble acid salt of sulfjirous acid and 'wherein Ar is a divalent phenylene radical cona member selected from thegroup consistingof j taining a sulfcnic acid group in the 2-position formaldehyde, acetaldehyde, jbenzaldehyde and and being otherwise free from substituents, An furfurol. is a divalent phenylene radical free from '7. A process for the manufacture of a water-H substituents, R is a member selected from the soluble salt of the aminostilbenederivative of o group consisting of H and lower alkyl, n and the formula m are whole numbers amounting to at most noas- CHr-N[ t-HNQt-NHCE v OzH HmS-G T-EQ-tt-HNQE-NHQ H which comprises condensing 4:4'-bis-[4:(4- 3, and z is a member selected from the group amino benzoylamino) benzoylamino] stil consisting of bene-disulfonic acid-(212') with a water-soluble condensation product from a water-soluble acid salt of sulfurous acid and formaldehyde.

8. A water-soluble alkali salt of an aminostilbene derivative of the general formula L l L 'TV wherein Ar is a member selected from the group Tl 10. A water-soluble alkalisalt ofLan-amino stilbenerderiveitiv'e ofthe general 'frmula,

1 wherein Ar is a. divalent phenylene radical containing a. sulfonic acid group in the 2-position 16 where Ar is'e. divalent plienyleneradical con-'- taining a, sultenic acid group in the Z-pdsition I and being otherwise free from substituents and An is a divalent phenylene radical free from and, being therwise free fromv'substituerits, and suhstituents. e,

An'ji's fl v lln j hehyl'e e, adicalif .f q fi i ii. A water -sdluble alkali salt 6f the ahiino-' stilbene derivative of the formula 12. A weter fsoluble alkali salt of an amino- E: stllbene derivative of the general formula,

, 13. A wateresoluble ,alkali salt ofltlie aminos'tilbene derivative jofthe formula v r 0 v FRANZ ACKERMANN.

** I I REFERENCES m file of patent! 1 The following reierences are 4 of cori m-, the

@UNITEE' SLTATES PATENTS Number Name Date 1,497,262 -Ev ans i r June 10, 1924 2,214,527 Green et all; Sept. 10, 1940 -2,248,'283 Rai ziss et al.: Ju ly 8, 1941 E 2,267,748 Poh1s" et a1 Dec. 30, 1941 l OTHER} REFERENCES st bpe grai Berjv. 46 (-1913), pp. 1226-1238. 

1. A PROCESS FOR THE MANUFACTURE OF A WATERSOLUBLE DERIVATIVE OF AN AMINOSTILBENE, WHICH COMPRISES REACTING AN AMINOSTILBENE OF THE GENERAL FORMULA 